Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
  • C08J5/122—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives using low molecular chemically inert solvents, swelling or softening agents
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/02—Halogenated hydrocarbons
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
  • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
  • C08L27/18—Homopolymers or copolymers or tetrafluoroethene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
  • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
  • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
  • C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
  • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S428/00—Stock material or miscellaneous articles
  • Y10S428/913—Material designed to be responsive to temperature, light, moisture

Definitions

• This invention relates to new polytetrafluoroethylene compositions and processes for making same. More specifically the invention relates to polytetrafluoroethylene compositions containing as a plasticizer therefor a chlorofiuoro telomer.
• Polymerized tetrafiuoroethylene and the method for preparing it are disclosed in U. S. Patent 2,230,654.
• This polymer is inert to most chemical reagents and is insoluble in all known solvents. Because of its inertness to solvents and other chemicals as well as to heat, polymerized tetrafluoroethylene is a very valuable material. However, due to its toughness, inflexibility, and low plasticity even at high temperatures the usual methods for molding and extruding plastic materials are impractical or uneconomical. Therefore, special techniques are required for shaping this polymer into even very simple forms.
• perfluorocarbon oils plasticize polytetrafluoroethylene, they are relatively ineffective for polychlorotrifluoroethylene which absorbs reasonably large amounts of perfiuorocarbon oils fairly rapidly, with higher temperatures increasing the rate of absorption.
• the products differ from polytetrafluoroethylene plasticized by these same oils in being hard and non-pliable at room temperature. Hence, one cannot predict what materials will plasticize one of these polymers from those which plasticize the other.
• a plastic composition consisting essentially of a mixture of from 91% to about 60% by weight of polymerized tetrafiuoroethylene, which normally fails to soften at temperatures below 327 C., and from 9% to about 40% by weight of a plasticizer of the class consisting of reaction products of chloroform with a member of the group consisting of chlorotrifluoroethylene and mixture of chlorofiuoroethylene with tetrafluoroethylene in which the tetrafiuoroethylene is present in a proportion of up to about 30% by weight, based on the combined weights of said two fiuoroethylenes, and such reaction products in which the hydrogen and from 1 to 3 chlorine atoms have been replaced by fluorine; which plasticizer boils at a temperature of at least C. under a pressure of 1 m. of Hg, has an average chain length of from about 25 to about 35 carbon atoms, and contains from about 20% to about 41% by weight of chlorine.
• plasticizer is 2025% by weight based on the total plasticized polytetrafiuoroethylene composition.
• plasticizers vary in consistency from oils to greases and have an average molecular weight of from about 1200 to about 2000. Since they are reaction products formed between a polymerizing monomer and a nonpolyrnerizable compound (in this case chloroform), these plasticizers comprise one of the types of products, referred to in this art as telomers, by which name they will often be referred to in this specification. Smaller amounts of plasticizer below 9% do not plasticize polytetrafluoroethylene satisfactorily for molding and extruding.
• telomer plasticizer content of the plasticized polytetrafluoroethylene compositions of this invention is reduced substantially by volatilization of the telomer grease or oil at 340360 C. These telomer losses are approximately 10%50% of the original telomer, being in the upper portion of this range for crude telomers.
• the unstabilized telomers are not necessarily more volatile than those remaining after the stabilizing treatment, but they are believed to be much more unstable to heat. Thus, although the molding conditions nearly eliminate loss of stabilized telomer, they cannot prevent substantial loss of unstabilized telomer.
• telomers Either stabilized or unstabilized telomers may be used in the practice of this invention.
• a stabilized telomer is one which has been heated to an elevated temperature in the presence of CoFa with agitation until the labile hydrogen and chlorine atoms (assumed to be one terminal H atom and three terminal Cl atoms) in the telomer have been replaced with fluorine atoms.
• the completion of this fluorination reaction was determined by the color change of the mass, which is caused by a change from CoFa to COFz (brown to pink).
• the desired degree of thermal and chemical stability in the telomer determines the extent to which the crude telomer must be treated.
• a satisfactorily stabilized telomer is obtained according to the procedure given below, where no further reaction occurs after two hours at 180220 C.
• the amount of chlorine in the telomer which may vary from 20-41% by weight, is indicative of the extent to which the crude telomer has been stabilized by treatment with COFs.
• the lower range of chlorine content applies to the stabilized telomers whereas the upper range of 41% chlorine applies to the unstabilized telomers.
• the larger the amount of tetrafluoroethylene used in making the telomer the lower the chlorine content of the crude telomer.
• the amount of chlorine in each telomer is actually determined by gravimetric analysis, and the molecular weight calculated from the chlorine content, assuming that the stabilized telomers contain one Cl atom for every two C atoms (the remainder being F atoms), and the crude unstabilized telomers contain three additional Cl atoms and one H atom per telomer molecule. For both stabilized and unstabilized telomers it is assumed that the ratio of tetrafluoroethylene to chlorotriffuoroethylene is the same in the telomer as in the mixture of monomers.
• telomers may be fractionally distilled and usedas man row cuts, or they may be used as crude telomer mixtures of different molecular weights, which are less expensive; or, of course, several diiferent purified telomers may be blended before use. In each of these three forms, however, the telomers are of substantially equivalent plasticizing value when mixed as indicated with powdered poly-tetrafluoroethylene.
• the tetrafluoroethylene content in the telomer should not exceed about 30% by weight based on the combined weights of the two fluoroethylenes, because larger amounts of tetrafluoroethylene in the telomer produce waxy or solid products which are not as satisfactory as plasticizers for polytetrafluoroethylene.
• the chlorofluoro telomers used in the practice of this invention maybe prepared, in general, by heating chlorotrifluoroethylene or a mixture of chlorot-rifluoroethylene and tetrafluoroethylene (said mixture containing up to 30% by weight of tetrafluoroethylene) in excess chloroform solution %-20% by weight total fluoroethylene concentration) containing 5%-1*0%, by weight of the totalfluoroethylene, of a peroxy catalyst, according to the method described by Miller et al., Ind. and Eng. Chem 39, 333 (1947).
• Suitable peroxy catalysts include ben-zoyl peroxide, acetyl peroxide and chloracetyl peroxide.
• the reactants are heated toa temperature sutficient to activate the particular catalyst used, which for benzoyl peroxide catalyst may be in the range of- 70 C.-l50 C.
• the reaction is continued until the drop in pressure levels off.
• a typical example of the preparation of a suitable chlorofluoro telomer involved the polymerization of 80- parts of chlorotrifiuoroethyleneand 20 parts of tetrofluoroethylene in 900 parts of chloroform at 100 C. using 5- parts of benzoyl peroxide catalyst. This reaction produced 85 parts of chlorofluorotelomer grease which has an average molecular weight in the range of 1200-2000;
• a typical example of stabilizing a chlorofluoro telomer following the general procedure described by Miller et al. (ibid.), involved heating the above telomer grease with slow agitation in a stainless steel, nickel or other corrosion-resistant vessel to a temperature of 135 C., at which point the first addition of CoF'a was made. CoFs was added in small portions over a period of 3.5 hours. The tot-a1 amount of'CoFa added was equal to the weight of the crude telomer to bestabilized, andthe extent of heating was determined by color change of the mass during. fluorination, the end of the stabilization treatment being achieved when the color had changed frombrown to pink (caused by change from COFs to CoFz).
• the chlorofluoro telomer plasticizers may be incorporated into the tetrafiuoroethylene polymer by either of two methods: (1) by a simple dipping of themassivepolymer (sheets, strips, rods, etc.) into liquid chloro- 4 fiuoro telomer maintained at 300 C.360 C. for /2 to 1 hour; or (2) by mixing a solution of the telomer plasticizer in a suitable solvent with the polymer molding powder or finely divided polymer.
• the polytetrafluoroethylene used may be either the white granular powder resulting from the polymerization of tetrafluoroethylene by well-known procedures such as that described in U. S. P.
• 2,393,967 or may be the finely divided colloidal particles of polytetrafiuoroethylene resulting from coagulation and drying of an aqueous colloidal dispersion of polytetrafluoroethylene, which in turn may be prepared by procedures, such as described i-n U. S. Patents 2,534,058 and 2,559,752.
• Suitable solvents which may be employed in working with these telomer plasticizers include 1,l,Z-trichloro-1,2,2-trifluoroethane, carbon tetra chloride, and other organic solvents in which the telomers are at least moderately soluble. Evaporation of the solvent leaves the telomer evenly distributed throughout the molding powder and plasticization is completed by heating at 340-360 C. for 10-15 minutes at 500 lbs./ sq. in. pressure. This combined heating and pressing procedure gives a satisfactory molding simultaneously.
• the chlorofluoro telomer was dissolved in trifluorotrichloroethane as a solvent (about 10-25 parts of solvent for each part of telomer). This solution was mixed with the polytetrafiuoroethylene molding powder, and the solvent was evaporated so that the particles of molding powder were coated and/ or impregnated by the telomer plasticizer. The resulting powder was loaded into a plain disc mold of such dimensions that a disc of 2% inch diameter with inch thickness was produced. This mold required a loading of 45-50 grams of powdered polytetrafluoroethylene, and was held at 340-360 C. for 10-15 minutes under 500 lbs/sq. in. pressure.
• the plasticized discs were tested for flexibility by manual examination, and for hardness by use of a Shore D scale durometer, a well-known instrument for measuring the hardness of soft materials. This is done by measuring the penetration into the object being tested with a pin of a certain diameter at an arbitrary calibrated loading on a spring. Thus, the smaller the Shore hardness value, the softer the plasticized polytetrafluoroethylene.
• Flanged couplings of plasticized polytetrafluoroethylene were also prepared. They were short pipe-like pieces about 1 in. in diameter with a small flange at one end in a plane perpendicular to that of the tubular portion. These were prepared in a suitable mold under the same conditions of temperature and. pressure used on the discs. These couplings were only /8 in. thick, and the effect of the plasticizer was even more strikingly observed than in the discs. Merely the pressure of the thumb and two fingers would bend these plasticized couplings, but not similarly-made unpl'asticized couplings. Furthermore, the plasticized couplings. exhibited a smooth, uniform surface in contrast to the chipped, uneven surface of the unplasticized ones.
• the present bonding procedure comprises applying the chlorofluoro telomer to the surface of polytetrafiuoroethylene sheets or other objects, which are then joined and heated under pressure to form the bond.
• the chlorofluoro telomer may be used as such, but it is more convenient to handle as a paste made-by flushing a polytetrafluoroethyl'ene dispersion into it.
• the telomer or telomer/polytetrafluoroethylene paste maybe applied byany convenient method such as brushing; A one minute heat treatment at approximately 200-500 lbs/sq. in. pressure gives satisfactory adhesion. Heat tteatments of less than one r'riinute are generally too short, whereas longer periods are unnecessary and would be harmful in that too much plasticizer would be lost by distillation from the polytetrafluoroethylene. Pressures lower than 200 lbs. per sq. in. require uneconomically long heating periods, whereas higher pressures than 500 lbs. per sq. in; are operable but unnecessary.
• the bonding strengths reported below were tested on a modified Schopper machine, which is an instrument for evaluating such adhesive bonds by pulling the members of the bonded article in opposite directions. The pull required to break the bond is indicated on a scale in pounds per linear inch.
• Example I Polytetrafluoroethylene powder (80 parts) was treated with parts of chlorofluoro telomer grease as a dilute solution in 1,2,2-trifluoroethane.
• the chlorofluoro telomer grease was made according to the above-described procedure from 80 parts by weight of chlorotrifluoroethylene and 20 parts by weight of tetrafluoroethylene. This grease had a chlorine content of 29.3% and an average molecular weight of 1800.
• the polymer contained 20 weight percent of telomer grease.
• a sample of this mixture was molded as described above (340-360 C. at 500 lbs/sq. in. for 1015 min.), producing a disc containing 16 weight percent of grease. This disc had a Shore hardness of 50.
• a Shore hardness of 40 resulted from use of 25 weight percent (20% after molding) of the same chlorofluoro telomer grease which had been stabilized by CoFa treatment, and fractionally distilled to produce a greasy cut having a chlorine content of 23.3% and an average molecular weight of 1200.
• Relatively soft couplings were produced from plasticized polymer containing 13 and 20 weight percent of unstabilized telomer grease and of a stabilized telomer grease, respectively. These couplings could be bent easily, as by the pressure of the fingers, whereas unplasticized controls were hard and stilf.
• Example 111 A 30 g. sample of a 50% polytetrafluoroethylene aqueous dispersion was flushed into 50 g. of chlorofluoro telomer, made from 80% chlorotrifluoroethylene and 20% tetrafluoroethylene in chloroform, by stirring at 50 C. in the presence of acetone. The volume of acetone used was approximately equal to the volume of the aqueous dispersion. Vigorous stirring of this mixture transferred the polymer to the grease phase to form a smooth white sticky paste, which was separated from the aqueous phase.
• This paste was brushed in a thin, even layer on to sheets of polytetrafluorethylene, which were subjected to a heat treatment of 340 C. at 500 lbs. per sq. in.
• the resulting bond had an average strength of 30 lbs. per linear inch as compared with 12 lbs. per linear inch for two pieces of polytetrafluoroethylene sheeting bonded at 350 C. without the adhesive paste.
• Example IV Another bond was made from a similar adhesive using the same procedure as given in Example III, but containing a CHC1 telomer grease of chlorotrifluoroethylene/ tetrafluoroethylene in the weight ratio of 70/30. In this case the average strength for sheets of A", and /2 was 26 lbs., as contrasted to 12 lbs. for the above mentioned control.
• Example V A chlorofluoro telomer was prepared by polymerizing chlorotrifiuoroethylene monomer in excess chloroform solution under the same conditions as described in Example I. The resulting telomer was stabilized by COF3 treatment as described elsewhere in the specification to give a product from which was separated an oil having a boiling point of -220" C. at 1 mm. of Hg and a chlorine content of 29.5%. 25 parts of this stabilized telomer oil were incorporated into 75 parts of granular powdered polytetrafluoroethylene by method (2) described herein; i. e.
• telomer content had dropped from 25% to 16% by weight.
• Shore hardness of this molded sample was 38 compared with 55 for unplasticized polytetrafluoroethylene.
• the plasticized polytetrafluoroethylene compositions of this invention permit the preparation of shaped articles possessing even greater softness and flexibility than unplasticized polytetrafiuoroethylene moldings and extruded objects. Furthermore, the stabilized telomers are considerably more effective than the perfluorocarbon oils of U. S. P. 2,510,078 for softening polytetrafluoroethylene, and the unstabilized telomers are slightly more effective. The amount of hydrogen in the crude chlorofluoro telomers is so small that it has a negligible elfect on the chemical resistance of the plasticized polymer article. In the stabilized telomers essentially all hydrogen has been replaced by fluorine.
• chlorofluoro telomers particularly in combination with finely divided polytetrafiuoroethylene, as adhesives for joining polytetrafluoroethylene to itself leads to substantially stronger bonds which cannot be obtained by heat-sealing this polymer alone.
• Another advantage of this invention is that the chlorofluoro telomers do not discolor polytetrafluoroethylene seriously, particularly if the telomers have been pretreated with CoFs.
• a plastic composition consisting essentially of a mixture of from 91% to about 60% by weight of polytetrafluoroethylene, which normally fails to soften at temperatures below 327 C., and from 9% to about 40% by weight of a plasticizer which is a member of the group consisting of 1) telomers of chloroform with chlorotrifluoroethylene, (2) telomers of chloroform with chlorotrifluoroethylene-tetrafluoroethylene mixtures in which the tetrafluoroethylene content does not exceed 30% by weight based on the combined weights of said two fluoroethylenes, (3) and compositions which differ from the aforesaid telomers in having hydrogen and from 1 to 3 chlorine atoms replaced by fluorine, which plasticizer boils at a temperature of at least 100 C. under a pressure of 1 mm. of Hg, has an average chain length of from about 25 to about 35 carbon atoms, and contains from about 20% to about 41% by weight of chlorine.
• a plastic composition consisting essentially of a mixture of from 91% to about 60% by weight of polytetrafiuorocthylene, which normally fails to soften at 7 temperatures below 327 C., and from 9% to about 40% by weight of a reaction product of chloroform with a mixture of chlorotrifluoroethylene with tetrafiuoroethylene iniwhich the tetrafiuoroethylene is present in a proportion from 20% to 30% by weight, based on the combined weights of said two fluoroethylenes, which reaction product .boils at a temperature of at least 100 C. under a pressure of 1 mm. of Hg, has an average chain chlorine. 7

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  • 1952-01-26 US US268464A patent/US2720498A/en not_active Expired - Lifetime
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